• Nenhum resultado encontrado

Ésteres Etílico e Metilico de GHB: Síntese, Estabilidade e Lactonização

N/A
N/A
Protected

Academic year: 2021

Share "Ésteres Etílico e Metilico de GHB: Síntese, Estabilidade e Lactonização"

Copied!
89
0
0

Texto

(1)

! ! " # $%%&

(2)

' ! " !

(3)

# $ % % &

(4)

'( )*+,(- $

# " ) $

. &/

0 ) # $ 1234#5

(5)

( )

%

" # #

(6)

vi *+ " #6*) ) -8) (# # ! " ; & #9 : 8 # & # $ * # " < & = " # # # " # # " 8 # > & ! ! # ! # & = ! ? 0 # # # & = ! " ) @ ( < & = &A) # # !$ ; B # # > # # 7 & =C #! ! . # 7 ; $ #! " # < # # . 7 & 6 # # % ; 7 # ' ./ 7 & < & * % % % " 2 # # #- % #* < # # ! # ) ! 7 &

(7)

vii = ! !# > % & 6 $ ) " ) 0 & ) $ < $ & % ! 7 " & D "

(8)

viii , ( C,0 C0? < 7 # # ' / ' / ; $ . & ) ! % B # # # # " '" /& * $ # B % # & ; # C,0 C0? B ! $ 2 E" E" & * $ # 7% B " B 7 C,0 C0?& + " $ ! C0? 7 $ $ B 85# 3,- +#3F - + * & C,0 C0? > B # B " ! CE* & ( $ 7 ! > 8 ,& C,0 C0? ! ,& ! E " E" > B B $ $ & ! ! C0? E"

E" ; % CE* &

* ! % <

CE* & G ! . !

(9)

ix * C,0 C0? :" : : " # & " : ! & " ! " H I" " " " " " " # " & " " " " " # " H I" " : # " " " I & 8 " H ! #C,0 C0? ! " ": E": : : ": E ": : : & " % : " " : ! C,0 C0?#! 7: ": : & " I H " I " : " :C0? ! " " 7 : " 8-#3,+ #3F + -)& " C0? C,0 : " # " 0 7 I C E )& " " I " 8 , & " !C0? C,0 , I & " ": E": : : ": E ": : : ! :7 & 8 I ! C0? ! ! " ": E ": : : ": E": : : " C E ) ; & " ! " H I" :7 " C E )& " ! ! # " # !! : &

(10)

-.(/0 JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ - JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ ) JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& 8K 8 JJJJJJJJJJJJJJJJJJ&JJJJJJJJJJJJJJJ3 3& 8 JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJL

3&3& M E" JJJJJJJJJJJJJJJJJJ&&JJJJ& F

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

F&N&3& E" * JJJJJJJJJJJJJJJJ&& 3S

F&N&L& E" JJJJJJJJJJJJJJJ&& 3N

F&O& * * C0? C,0JJJJJJJJJJJJJJJ3O

F&O&3& * C0?JJJJJJJJJJJJJJJJJJJJJJ& 3P

F&O&L& * C,0JJJJJJJJJJJJJJJJJJJJJJ3P

F&P& * ? 7 G JJJJJJJJJJJJJJJJJJL4

(11)

S&3& ) E" * E" JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& LL S&L& 7 * * E" * E" JJJJJJJJJJJJJJJJJLF S&L&3& * ! 8! " JJJJJJJJJJJJ&&& LF S&L&L& - < $ + JJJJJJJJJJJJJJJ&&& LS S&L&F& * JJJJJJJJJJJJJJJJJJ&J& LO S&F& * C,0 C0? > B J&J&& LT

S&S& $ C,0 CE* J&&& NN

88K JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& OT

N& JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&&& O1

(12)

-.(/0 ( !/ ,* '* * !+ !+ 12* C,0 ! ! B &&&&&&&&&&&&&&&&&&&&&&&&&&&&&F !+ $2 * C0?&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&& N !+ 22 Interconversão do GHB em C0?JJJJJ&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&& O !+ 32 ! C0?JJJJJJJJJJJJJJJJJJJJJJJJ&&J&& O !+ 42 B ! JJJJJJJJJJJJJJJJJJJJJJJJJ&&JJ& P !+ 52 *% % ? *&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&& 1 !+ 62- 7 C,0 0) U 3V ) JJJ&&JJJJJ34 !+ 72 * E" JJJJJJJJJ&&J&&&&&&&&&&&&&&&&&& 3N

!+ &2 * E" JJJJJJJJJJJJJJ&&&& 3O

!+ 1%2 ! 7 C0? $ C,0JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ3P !+ 112 C0? !B -WT#3F JJJ&&& 3T !+ 1$2 ! 7 C,0JJJ& 31 !+ 122 C,0 -W34#LL J& 31 !+ 132 LE" B - W34#ON JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJL4 !+ 142 E" -W1#NO &&JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ& L3 !+ 152 E" -WT#TT JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJL3 !+ 162- ! E" JJJJJJJJJ&& LL !+ 172 - ! E" JJJJJJJJJ& LL

!+ 1&2 ! E" Q-WN#SO R JJJ& LL

!+ $%2 ! E" Q-WN#SP R JJ& LF !+ $12* ! " E" J&&& LF !+ $$2 * ! " E" & LN !+ $22 3,- + E" JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& LN !+ $32 3F - + E" JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&&JJJJJJJJJJJJ&LN !+ $42 3,- + E" JJJJJJJJJJJJJJJJJJJJJJJ&&JJJJJJJJJJJJJJJJJJ&& LN

(13)

!+ $52 3F - + E"

JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJLO

!+ $62* Q8*R E" JJJJ&JJ&&&&& LP

!+ $72 * Q8*R E" JJJJJJ& LP

!+ $&2 - ; ?!! : E" JJJJJJ&& LT

!+ 2%2 X7WTP E" JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& LT !+ 212 " $ $ C,0 B JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ& L1 !+ 2$2 C,0 JJJJJ&&JJJJJF4 !+ 222 C,0 ,L JJJJJJJJF3 !+ 232 C,0 JJJJJJJJJ&& F3 !+ 242 C,0 ,L JJJ&&JJJ& FL !+ 252 C,0 " JJJJJJJJJJJJJJJJJJJJFF !+ 262 C,0 W4 > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& FF !+ 272 C,0 WPL" > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& FF !+ 2&2 C,0 ,L W4 > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ& FS !+ 3%2 C,0 , L W3L4" > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJFS !+ 312 C,0 W4 > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&J& FN !+ 3$2 C,0 W3OT" > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ& FN !+ 322 C,0 , L W4 > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&&J&& FO !+ 332 C,0 , L W1O" > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&JJ&& FO !+ 342 C,0 " W4 > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& FP !+ 352 C,0 " W3SS" > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&JFP !+ 362C ! C0? JJJJJJJJJJJJJJJJ&&JJJJJJJJ& F1 !+ 372 C ! C0? ,L JJJJJJJJJJJJJJJJJJJ&&&&&& F1 !+ 3&2 C ! C0? JJJJJJJJJJJJJJJJJJJJJJJ& F1

(14)

!+ 4%2 C ! C0? ,L JJJJJJJJJJJJJJJJJJJ&& S4 !+ 412C ! C0? " JJJJJJJJJJJJJJJJJJJJJ&JJ&& S4 !+ 4$2 ! C0?JJJJJJJJJJ&&& S3 !+ 422 $ C,0JJJJJJJJJJJJJS3 !+ 432 C0? W4 > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJSL !+ 442 C0? W3L4" > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& SL !+ 452 C0? W4 > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ& SF !+ 462 C0? W1O" > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&&JJJSF !+ 472 C0? W4 > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& SS !+ 4&2 C0? WPL" > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ& SS !+ 5%2 C0? , L W4 > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJ&JJJJJJJJJSN !+ 512 C0? , L W3OT" > CE* 7 " JJJJJJJJJJJJJJJJJJJJJ&&JJJJJJJJJJ&& SN !+ 5$2 C0? " W4 > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJSO !+ 522 C0? " W3OT" > CE* 7 " JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ& SO !+ 532 C ! ? C0?JJJJJJJJJJJJJJ&&JJ& S1 !+ 542 C ! ? C,0JJJJJJJJJJJJ&&JJJJ& S1 !+ 552 C ! ? LE, B JJJ&&JJJJJ&& S1 !+ 562 C,0 $ JJJJJ&JN4 !+ 572 ! $ C,0 JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJNN

!+ 5&2 E" > CE*

7 " Q-C0?WT#FF R JJJJJJJJJJJJJJJJJJ&& NO

!+ 6%2 E" > CE*

7 " Q-C0?WT#F3 R JJJJJJJJJJJJJJJJJJ& NO

!+ 612 E" !B

(15)

!+ 6$2 E" !B Q ; W3N4Y Z- C0?WT#31 Z- G C,0W1#NP R JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&J& NT !+ 622 E" !B Q ; WT4Y Z-G C,0W1#O4 R JJJJJJJJNT !+ 632 E" !B Q ; WLN4Y Z-C0?WT#L3 R JJJJJJJJJ&JJJJJ&& N1 !+ 642 E" !B Q ; W3N4Y Z-C0?WT#L1 R JJJJJJJJJJJJJJJN1 !+ 652 E" !B Q ; WT4Y Z- C0?WT#4P Z- G C,0WT#TL R JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& O4 !+ 662 E" Q ; WLN4Y Z-C0?WT#LF R JJJJJJJJJJJJJJJO3 !+ 672 E" Q ; 3N4Y Z- C0?WT#3O Z- G C,0W 1#P4 R JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& O3 !+ 6&2 E" Q ; T4Y Z-G C,0W1#NO R JJJJJJJOL !+ 7%2 E" ELE Q ; LN4Y Z-C0?WT#FP R JJJJJJJJJJJJJJJOL !+ 712 E" ELE Q ; 3N4Y Z-C0?WT#F3 Z-G C,0W1#P4 R JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& OF !+ 7$2 E" ELE Q ; T4Y Z-G * C,0W1#LP R JJJJJJ& OF !+ 722 E" Q ; LN4Y Z-C0?WT#F3 R JJJJJJJJJJJJJJOS !+ 732 E" Q ; 3N4Y Z-C0?WT#L4 Z-G C,0W T#1O R JJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJJ&& OS !+ 742 E" Q ; T4Y Z-G C,0WT#TT R JJJJ& ON !+ 752 E" ELE Q ; LN4Y Z-C0?WT#N4 R JJJJJJJJJJJJJON

(16)

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

' &2 - LE" B JJJJJJJJJ&&JJJJJJ&JJJ&& N3

' 1%2 - C,0U LE" B JJJJJJJJ&JJJJJJ&& NL

' 112 8 $ C0?JJJJJJ&JJJJJJJJJJ&JJ&JJJJ&& NL ' 1$2 8 $ C,0JJJJJJJJJJJJJJ&JJ&JJJJJJ&& NL ' 122 * C,0 JJ&JJJJJJJ&&J&JJJJJJ&& NF ' 132 * C,0 , WL JJJJJJ&JJJJJJJ&& NF ' 142 * C,0 JJ&JJJJJJJ&J&&JJJJJ&& NF ' 152 * C,0 , WL JJ&JJJJJ&&JJJJ&& NF ' 162* C,0 " JJ&JJJJJJJJJJJJJJ&& NF ' 172 * C0? JJ&JJJJJJ&&JJ&JJJJJJ&& NS ' 1&2 * C0? , WL JJ&JJJJJ&JJJJJJ& NS ' $%2 * C0? JJ&JJJJJJJ&&&JJJJJJ&& NS ' $12* C0? , WL JJJJJJ&JJJJJJ&& NS ' $$2 * C0? " JJJJJJJJJ&&J&JJJJJJ& NS

(17)

* # 3#S 0 K 3#SE 0) K +E(E E ! C K ! C ?K ! ?% ? *K ! ?% *! . * K * K C 0 K \E C0?K E C,0K M E" 85E 8! " ) K E+E ! +8 K + * ( ) K ( 7 ) ] - + K - < $ + ? K ! ) E 5K E

(18)

3

0 8 /

(19)

L 19 / < % . # " & ) . ! & ) B ( 7 ) ] Q( )R L44L#T#1V . < ^3_& ( 8 + * Q+8 R ! ' / " . % ; # # ' / ' /& ( C,0$ ^L_& ( M E" QC,0R $ & G B # & L44L # # $ * . & ) $ T4 ! $ 14 ! * #* ^FES_& C,0# C,0 E QC0?R 3#SE Q3#SE 0 R ^N_& ] 34 " 7 ^O_& ( C,0 ! 7 % 7 # $ # ! & # 7 . & + ! # < $ ! %` # B ^P_& 8! > B ! - # #* % % > . C,0& # . % ! ! ! ! . #

(20)

F ! ! X ^O_& * % # C,0 C0? ! & C0?$ C,0 " B % C,0 ! ! C0?& * B # C0? ! $ C,0# B # ! & # C0? ! C,0 % C0? ! $ C,0 B # X & # E > $ C,0# % C,0$ < C0? # 8 #? ) $ ^F#T_& #$ C,0 C0? B 7 $ % & 1919 : ; < ( K" QC,0R SE" B Q 3R# $ $ " K" & G < < #% S ! 2 & G < # & + ! $ % & + ! B $ B & ) !B $ S,T(F 34S#3& ( C,0# ! #% ! #$ ] ] < ^1E34_& ( 9 C,0$ S#PL& 32 * C,0 ! ! B & G < #% ! # $ # > " #" # < < &

(21)

S X B ^33E3L_& * % \E QC 0 R# \E QC0?R 3#SE Q3#S 0 R& # " B C,0 $ 31O4# % B ? 7 C,0 ; < % 7 C 0 % " ! ! # 7 > ^33E3L_& + * 6 # C,0 ! 7 C 0 ! $ # 7 # 7 ! $ ! & # 7 * # . ^S#3LE3F_& + * # % % % " a #! ^3F_& # Q R 7 b: c ^3SE3N_& ! ! . # C,0 ; % 7 # F#SK ! Q* :R ^3O_& $ # 7 $ ^3S#3P_& C,0 ! B $ & # $ & ( C,0 ! % # B > ^3O#3T_& + # ! ! . C,0 7 b: c^31_& ( C,0$ % " # ^L4_& ) ! ! & 7 ! N1 K ONV& " % " % C,0$ 7 #

(22)

N ^L3_& ( " ! 3N SN B ^LL_& B C,0$ 7 B + U " C,0 & ( 7 7 7 C,0 $ C,0 E" #% $ 7 ! & ( 7 C,0 $ 7 + U % $ & ( $ ! 9 #% ! $ 7 (L ,L( ^L3_& 6 ! $ C,0& ( $ C,0 $ ^LF_# 7 ^LS_ ! ^LN_& * $ 7 C,0 ! QC R ! % ! . Q ? *R& # $ C,0 Q3#SE0 C 0 R# $ C & $ 7 $ ! E & , . E % # # E+E ! Q ) R +E(E E ! Q0) R ^LO_& 19$9 γγγγ; γE0 QC0?R Q LR $ % # " & ) !B $ S,O(L TO#41#

3#3L X ? LNY L4S E L4NY & G ]

] # # # $ 7 ^1#LP_&

(23)

O G $ C,0& * % # % ,E $ < " & * C,0 % ! $! Q FR ^LT_& F2 8 C,0 C0?& C0? 7 \E ! C,0 !$ & ? # ! C,0 ^33_& C0? B , ! ! ! $ C,0 # Q SR ^L1_& S2 ! C0?& C0? C # 7% # ! % & ( $ C0? ? *X 5^LO_# $ ^LF_# & 1929 = 0 +"> ! $ % $ 7 ! # # B & G $ # < 7 ! # <

(24)

P ! % & $ ! # ! ! Q? R ] ^F4_& > Q #-R ! % ^F3_& $ ! % . E " $ 7 % % ! . # B % E % 7 ^FL_& 192919 0 + > + ! # 7 ; # ! ! & $! ! # "$ #% ! B & $ ! & $ ! B ! & ! ! # ; # ! #! # ! N ^F3#FFEFS_& N2 B ! 2 Q3R #QLR -#QFR 5 ! #QS#NR 8; #QOR #QPR #QTR #Q1R - & ^FS_

(25)

T 7% < ! # ; # % % & ( 2 % # # #! ! & , 2 7 " # $ # $ # ^FF_& ( 7 " $ < < & 7 " " . X ! & ( ] $ 7 " & G ^F3_& ( $ $ > $ % $ & G ! < ^F3_& ( $ 2 ! β# $ 7 Q . R ; $ ^F3_& % $ ! # ! 7 B & $ ! C K * & $ # ! % # B #$ & ! C K * $ % ! B ! a & 8 ! % ! " ! a a ^FF_& * ! !7 % B ! % 2 ?K * &

(26)

1 $ " ! CE* $ ! 7 ! > & ( a 7> E # X7&( Q R# # $ $ 7 % # 7 ! %`. & ( ; $ & ; $ 7 X ^F3_& ( CX* B ! $ $ ! C,0 C0?^LO_& 1929$9 0 + > ? ! ?% *! . Q ? *R 7 ! & G $ 7 # #! > % # % > < E ! ^F3#FN_& ! % 7 & ( ! 7 7 ! # # ; # # O ^FN_& O2 *% % ? *& K - B * #0K # K 5 # K #*K < # K 5 8; #C K ) #, K ? *#8K #6 K 8 ! #9 K

(27)

34 ? * E! B # E! ! B & ! > $2 ! ! #! B % ! Z ! ! #! % ! B Z a ^FN_& ( ? * 2 Q 5R# ! " Q85R# ! . # % # ! # ^F3_& ? *$ $ B B & G $ 7 ! C,0 C0?^LO_& 192929 ( # 7 $ 7 C $ 7 " $ # % ! # " ! ^FP_& + > 7 " . +,#(, ), % # & * > ! 7 < ^FT_& P2 - 7 C,0 0) U 3V )&

(28)

33 $9 @ A # ( C,0 C0? ! % B & 7 E # ;# # & * < E # CE* # ! $ C,0 C0? # & % . ; # $ 7 E" E" # 7 ! < & " ! $ % $ ! ! C0? % CE* 7 & ( ; % " % &

(29)

3L

0 8 //

(30)

3F 29 <8 2919 '= 0 +"> 291919 0 + > 0 ! ! ! #! 7 O4C Q? C- cR 4#L4 ! . LNS & !B & B# # ! < QλW LNS R ! $ & 2919$9 0 + > 0 7 " ! ! " QC - cR P4 X3N4 ?& 291929 0 + > ? * > B C0 * D > ? *#! 7 ! ,: ,F#LN4 S#O #N µ #,  ! !B ! B & 5X5 6 K LSN K TPN # 2 34 ; L4µ?#! 3 ?X & 29$9 '= 8 )8 29$919 / > # ( ! " Q85R ! 90# B 8 C 8-# 7 E !I d8+ 8-) F&44& 29$9$9 , E + = . ( < $ Q- +R ! % # # B 0 H F44& 7 E Q F ( FR& ( %

(31)

3S δ Q R Q )R ! . Qδ W4R# Q6R ! , 7Q,7R& 2929 0 + > ; 8 ( ! ; QC0? $ R B 7 QC,0 LE, B R % CE* # ! " @ *8 C L444 ) a " @ C @ & 2939 , + # , + * BK * , )B Q+ , (FR BK !B BK * * BK * C0?3 BK ) " C,0 EEEE ) L BK ) ! )B BK 3C0?! & L ^F1_ 32 - & 2949 = 294919 ; < E LN4 ! 1 ?Q4#3L R C0?#NF ?Q4#O1 R !] $ , 3& ; $ # E SN # % E ! 3 ,& E ! E " B $ , P& E E & ( !

(32)

3N ! QF444 #34 R ! ! Q " R # $ 2 !B QLN4 ?R# !B 323 QLN4 ?R QLN4 ?R& ( ! ! , ? ! Q ,: ,F# !B R# E " ! % N N#T & E F#OO % E" % ! 7 85#3,- +#3F - + * &

E" 2 2 FOV& ?% & 85

Q90R2 FS31#L1PP#L1FN#LTPP#3PLT#3OS3#3NL1#3SOP#3SSF#3FPL#3FSF#3F3F#

3LSO#33O4#34N1#34FL#1SF#13L#NP4#SNN#SFF E3&3,E- + QF44#3F ,7Z

F ( FR2 eWF#OF Q#3,#(,R#F#NP Q#L,#6 WO#F4 ,7#,fR#3#P1 Q%#

L,#6 WO#TT ,7#,gR#L#FT Q#L,#6 WP#SS ,7#,\R#S#41 Q%#L,#6 WP#3L ,7#

( ,L ,FR#3#LL Q#F,#6 W P#3S ,7 ( ,L ,FR& 3F E- + QPN#SP ,7Z

F ( FR2 e W 3PF#P Q (R#F3#L Q fR#LT#T Q gR#O3#S Q \R#O4#S

Q( ,L ,FR#3S#N Q( ,L ,FR& * 2 F1 Q344R#TP QOOR#3FF QFTR ^ U3_U&&

T2 * E" 2949$9 ; < E LN4 ! 3N ?Q4#3T1P R C0?#TN ?QL#411 R !] $ , 3& ; $ # E SN # % E ! 3 ,& E ! E " B $ , P& E E & ( ! ! QF444 #34 R ! ! Q " R # $ 2 !B QLN4 ?R# !B 323 QLN4 ?R QLN4 ?R&

(33)

3O ( ! ! , ? ! Q ,: ,F# !B R# E " ! % N N#T & E 1#P % E" % ! 7 85#3,- +#3F - + * &

E" 2 2 NPV& ?% &

85Q90R2 FS3T#L1ST#LTPN#3PLT#3ONS#3SFF#3FO4#3F3N#3LSO#331O#33N1#34NN#

13T#TPS#ONP#NOO#SLP E3&3,E- + QF44#3F ,7Z F ( FR2 eWF#P3

Q#3,#(,R#L#SS Q#L,#6 WP#SS ,7#,fR#3#P1 Q%#L,#6 WO#TO ,7#,gR#F#NP Q#

L,#6 WO#LT ,7#,\R#F#OL Q#F,#( ,FR&3F E- + QPN#SP ,7Z F ( FR2 e

W3PS#P Q (R#F4#1 Q fR#LT#T Q gR#O3#S Q \R#N3#P Q( ,FR& * 2 F1 Q344R#

TP QFOR#331 Q1R ^ U3_U&#&

12 * E" 2959 C0? C,0 > % # > " 7 ! ,& ! > & C0? Q34 X ?R ) B S4 VQXR ) B S4 VQXR , L ) B 4#41 VQXR ) B 4#41 VQXR , L " C,0 Q34 X ?R ) B S4 VQXR ) B S4 VQXR , L ) B 4#41 VQXR ) B 4#41 VQXR , L " L2 ) > C0? C,0&

(34)

3P 295919 > C0?! L N4 h !B & ! !B ! ! B #! L#4 ?& ( ! !B & * > C0? 3 X ?# % ! 7 CE* & 2959$9 > C,0! ; . Q7 R& ( ! $ > C,0 34 X ?& E > C,0 4#L X ?& * ! LE" B Q4#F X ?R# % ! 7 # ! ; 7 0) & > 7 ! 7 CE* & * " 8 0 ; ; 3 h > ! 7 & > C0?! ( ^F1_2 ; # ; LN4Y # ! SNY N L4Y $ ! LT4Y Q 34R& 342 ! 7 C0? $ C,0&

(35)

3T ( a ! 7 a P4 5& " ! . ! LT4Y ! a ! L44Y & ! # % ! 3N FL4 X7&* )8 Q) 8 R# ; ! " ! 2 X7WLT#S3#SF#TP#331 3FF& + > B # C0? ! T#3F Q 33R& 332 C0? !B -WT#3F & > C,0! ( ^F1_2 ; # ; LN4Y # ! SNY F 3NY $ ! LT4Y Q 3LR&

(36)

31 3L2 ! 7 C,0& ( a ! 7 a P4 5& " ! . ! LT4Y ! a ! L44Y & ! # % ! 34 FL4 X7&* )8 Q) 8 R# ; ! " ! 2 X7WSL#33O#3SP#3N1#L4S#LFL# LFF#LO3 F4S& + > B # C,0 ! 34#L LE" B ! 34#P ! 3F 3S& 3F2 C,0 -W34#LL &

(37)

L4 3S2 LE" B -W34#ON & 2969 7 $ C,0! > < N X ? 2 !B # & * " 8 0 ; ; 3 h > ! 7 & ! ; & ! . ; 7 $ #!

! 2 T4Y #3N4Y LN4Y &

! ! SNY N

L4Y $ ! LT4Y Q 34R&

( a ! 7

a P4 5& " ! . !

LT4Y ! a ! L44Y &

! # % !

34 FL4 X7#

Q)8 2 ) 8 R# % ! " ! 2 X7W

(38)

L3 + > B # $ C,0! 1#O $ C,0! T#1 ; T4Y Q 3N 3OR& 3N2 E" -W1#NO & 3O2 E" - WT#TT &

(39)

LL 39 , ( 3919 ; < ; < ! 0 I 9 : ^S4_& ( ! C0? B , & ( B $ . C0? % ! ^T_& ? # ! Q 3LR& ( ( U (, ,L)(S ,( ( ( 3P2 - ! E" & 3T2 - ! E" & + ! ? *#! " ! > ! 7& ! 31 L4& 312 ! E" Q-WN#SO R& 8 7 Q-W F#43 R&

(40)

LF L42 ! E" Q-WN#SP R& 8 7 Q-W F#4F R& 39$9 0 ; < ; < 39$919 8 > / > # ! L3 LL 85Q90R $ C,0 $ C,0# & L32 * ! " E" &

(41)

LS LL2 * ! " E" & + < $ ! 3PLT E3# E W( $ & ( K ( $ 33O4 E3 ( K , FS3T E3& ! $ ! 34N4 E3# K (,& > ! > > 2 K , QL1N4EL1P4 E3R K QP44 K 3F44 E3R& 39$9$9 , E + = . $ ! 3,- + 3F - +& ! LF 3,- + E" &

(42)

LN LF2 3,- + E" & ( 3,- + E" F44 ,7 F ( F F#OF " # F#NP 6 WO#F4 ,7 " . Ef# % 3#P1 6 W O#TT ,7 " . Eg# L#FT 6 W P#SS ,7 " . E\# % S#41 6 WP#3L ,7 " . Q( ,L ,FR 3#LL 6 WP#3S ,7 " . Q( ,L ,FR& ! LS 3F - + E" & LS2 3F - + E" & ( 3F - + E" PN ,7 F ( F e W 3PF#P !

#eWF3#L Ef#eWLT#T Eg#eWO3#S

E\#eWO4#S Q( ,L ,FR eW3S#N

Q( ,L ,FR&

! LN

3,- + E" &

(43)

LO ( 3,- + E" F44 ,7 F ( F F#P3 " # L#S4 6 WP#SS ,7 " . Ef# % 3#P1 6 W O#TO ,7 " . Eg# F#NP 6 W O#LT ,7 " . E\ F#OL " . Q( ,FR& ! LO 3F - + E" &

LO2 3F - + E" &

( 3F - + E" PN ,7

F ( F e W 3PS#P !

#eWF4#T Ef#eWLT#T Eg#eWO3#S

E\ eWN3#P Q( ,FR& 39$929 8 ! LP LT E" E" # # % CE* 7 " & E ! < & * ! ! % . $ # % . . ! U3 % & * ! !7 % # 7 # ; U3 % $ & + $ ! X7 $ ! &

(44)

LP T:+ c Full ms [ 15.00-320.00] 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 R el at iv e A bu nd an ce 43.1 55.1 39.1 87.1 45.1 61.1 73.1 74.1 69.1 75.1 133.1 115.1 38.1 18.1 31.1 88.1 102.1 131.1 134.1 186.3 254.2 174.9 196.9 303.0 149.3 216.1226.7 240.4 261.7 282.1 318.5 T:+ c Full ms [ 15.00-320.00] 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z 0 5 10 15 20 25 30 35 40 45 50 55 T:+ c Full ms [ 15.00-320.00] 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 R el at iv e A bu nd an ce 60 65 70 75 80 85 90 95 100 R el at iv e A bu nd an ce 43.1 55.1 39.1 87.1 45.1 61.1 73.1 74.1 69.1 75.1 133.1 115.1 38.1 18.1 31.1 88.1 102.1 131.1 134.1 186.3 254.2 174.9 196.9 303.0 149.3 216.1226.7 240.4 261.7 282.1 318.5 LP2 * Q8*R E" & T:+ c Full ms [ 15.00-320.00] 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 R el at iv e A bu nd an ce 43.1 39.1 57.1 87.1 55.1 69.1 101.1 38.1 83.1 88.1 119.1 59.1 74.1 19.1 33.1 89.1 102.1 120.2 146.2 163.4 173.0183.4195.5 211.7222.3236.7248.6 259.6 269.5 298.9310.5 T:+ c Full ms [ 15.00-320.00] 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z 0 5 10 15 20 25 30 35 40 45 50 55 T:+ c Full ms [ 15.00-320.00] 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 m/z 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 R el at iv e A bu nd an ce 43.1 39.1 57.1 87.1 55.1 69.1 101.1 38.1 83.1 88.1 119.1 59.1 74.1 19.1 33.1 89.1 102.1 120.2 146.2 163.4 173.0183.4195.5 211.7222.3236.7248.6 259.6 269.5 298.9310.5 LT2 * Q8*R E" & ( X7W33N X7W343 $ # &

(45)

LT + $ # X7WTP ; ! E QE ((R ,F ,L(# % Z X7WTT E ! 2 K ((, Q > ((, ! % $ R ; ?!! :Q L1R& L12 - ; ? !! : E" & + $ # X7WTP ; ! E ,F( Q F4R& F42 X7WTP E" & 3929 F ) ( C,0 C0? ! % B & 7% #% # Q$ R#$ % Q B R# > ! ! E" E " Q F3R

(46)

L1 F32 " $ $ C,0 B ! C,0 $ ! # % % ! C0? $ ! & + # # $ ! $ C,0 C0?# E > B B C,0 C0? E % < B # " & " # S4V # E # 4#41V& 7% , < % ! > ! ! # E > B B C,0 C0? , E > B B C,0 C0? , L& " , ! ! $ # 7% ! $ & * # > !

(47)

F4 4 $ L44 ,& + 3L " " E % 3 3 " & 3L " #! " % LS LS,& % ! CE* # > ; ! & E $ > % ! . ! ! . 7& # a ! E % # > ! # % % % % < ! C,0# C0?#$ C,0 $ C,0& * ! > $ " & ! $ ! 7 L ! 2 > C,0 C0? ! $ C,0& ! FL FO C,0 & % $% 3% 5% 7% %9%% %9%4 %91% %914 %9$% %9$4 ' 8 C D C +G D FL2 C,0 &

(48)

F3 8 $ % 4% 1%% 14% %9%% %9%4 %91% %914 ' 8 C D C +G D FF2 C,0 ,L & % 4% 1%% 14% $%% %9%% %9%4 %91% %914 %9$% %9$4 ' 8 C D C +G D FS2 C,0 &

(49)

FL 8 $ % 4% 1%% 14% %9%% %9%4 %91% %914 %9$% ' 8 C D C +G D FN2 C,0 ,L & 0 % 4% 1%% 14% $%% %9%% %9%4 %91% %914 %9$% Tempo (h) C +G D FO2 C,0 " &

(50)

FF

! FP FT B

C,0 7 PL " &

FP2 C,0 W4 > CE* 7 " &

(51)

FS ! F1 S4 B C,0 , L 7 3L4 " & F12 C,0 ,L W4 > CE* 7 " & S42 C,0 , L W3L4" > CE* 7 " &

(52)

FN

! S3 SL B

C,0 7 3OT " &

S32 C,0 W4 > CE* 7 " &

(53)

FO ! SF SS B , L C,0 7 1O " & SF2 C,0 , L W4 > CE* 7 " & SS2 C,0 , L W1O" > CE* 7 " &

(54)

FP

! SN SO C,0 "

7 3SS " &

SN2 C,0 " W4 > CE* 7 " &

(55)

FT ! Q FL SOR % " C,0# ! < & ! < % $ % C,0 CE* % " ; 7 & # < ! 7 & * # $ C,0& ( $ < , C,0& G ! % > , L#% B #% B # C,0 $ % > % ,& * ! E % C,0 # ! > & G $ ! % # > , L# C,0$ B % B & * ! ! % > % C,0 % & #$ % ,L C,0$ ! 344 " B ! 3L4 " B & ! SP N3 C0? &

(56)

F1 % 4% 1%% 14% %9% %9$ %93 %95 %97 19% ' 8 C D C +G D SP2 C ! C0? & @ 8 $ 0 50 100 150 0.0 0.2 0.4 0.6 0.8 1.0 ' 8 C D C +G D ST2 C ! C0? ,L& % $% 3% 5% 7% %9% %9$ %93 %95 %97 ' 8 C D C +G D S12 C ! C0? &

(57)

S4 8 $ % 4% 1%% 14% $%% %9% %9$ %93 %95 %97 ' 8 C D C +G D N42 C ! C0? ,L& 0 % 4% 1%% 14% $%% %9% %9$ %93 %95 %97 ' 8 C D C +G D N32 C ! C0? " & ! C0? $ ! # ; ! NL& + " ! $ $ & ^T_ $ C,0 C0?& ( ;# C,0 ! # ! C,0 C0?# % ! $ # Q NFR&

(58)

S3 NL2 ! C0?& & NF2 $ C,0& ^T_& ! NS NN B C0? 7 344 " &

(59)

SL

NS2 C0? W4 > CE* 7 " &

NN2 C0? W3L4" > CE* 7 " &

! NO NP B ,

(60)

SF

NO2 C0? W4 > CE* 7 " &

NP2 C0? W1O" > CE* 7 " &

! NT N1 B

(61)

SS

NT2 C0? W4 > CE* 7 " &

N12 C0? WPL" > CE* 7 " &

! O4 O3 B

(62)

SN

O42 C0? , L W4 > CE* 7 " &

O32 C0? , L W3OT" > CE* 7

" &

! OL OF C0?

(63)

SO

OL2 C0? " W4 > CE* 7 " &

OF2 C0? " W3OT" > CE* 7 " &

! Q SP N3R

Q NS OFR % " C0?#

! < #

(64)

SP # # % % 7 % < ! # $ C,0# % ; . % & * ! " # & ! # ^T_ ! $ > B ! & # ! % # > $ # ! # ! & ( ; & > C,0# < , C0? $ & G ! % > , L#% B #% B # C0? $ % > % ,& * ! E % C0? # ! > & $% # % > C,0# C0? > B $ % > B & * ! L & # % % > B # > S4V#! # > B # > ! # 4#41V# % ! ! & * ! B % # % % < # % & + " ; ! $ C,0 # % $ % & $ # % > C,0# C0? $ # ! 3N4 " &

(65)

ST * C,0 C0? " # ! E " % > < & , < & * $ " % > B # % ; ! % # % ! ! & # $ ! . ! < & ( $ E ! # ! % ! # # 7 % #$ . 7 $ % & ! < 8 ! , 7 Q8 ,R& ! # # # % ! # ! ^S3_& 8 > + ! " ! 7 & > C,0#C0?#LE, C,0 U LE , ! & E % -L $ % $ !* L44F& ) < ? Q X ?R *% - ! Q-LR C0? 4#N K L#PN :WF#4i34P U N#4 i34O 4#11F1 C,0 4#44NN K 4#F :WL#4i34T U L#4 i34O 4#11L M LE " B 4#3 K L :W3#4i34T E TN4LP 4#11T3 F2 [ #% ! C0?# C,0 LE" B &

(66)

S1 4 L4444444 S4444444 O4444444 T4444444 344444444 3L4444444 4 4#N 3 3#N L L#N F C +G D : OS2 C ! ? C0?& 4 3 4444444 L4444444 F4444444 S4444444 N4444444 O4444444 P 4444444 4 4#4N 4#3 4#3N 4#L 4#LN 4#F 4#FN C +G D : ON2 C ! ? C,0& $; < 8 ) 4 N4444444 344444444 3N4444444 L44444444 LN4444444 F44444444 4 4#N 3 3#N L L#N $; < 8 ) C +G D : $ ; < 8 ) OO2 C ! ? LE, B ( C,0! 7 $ & * % # C0?! 7 $ &

(67)

N4 ) < ? Q X ?R *% - ! Q-LR C,0U LE " B 4#44NN K 4#F :WN#OLF U 4#4P1T 4#11OT S2 [ # % ! C,0 U LE " B Q8R& H$; < 8 ) 4 4#L 4#S 4#O 4#T 3 3#L 3#S 3#O 3#T L 4 4#4N 4#3 4#3N 4#L 4#LN 4#F 4#FN C +G D : G : $ ; < 8 ) OP2 C,0 $ & ( ( ! !B 2 ? WF#FiσX)# 2σ $ ) $ ^S3_& ( 2 * * ,WL ,WL "

C0? S#NS i34ES S#OT i34ES S#P i34ES S#TS i34ES S#PS i34ES

C,0 3#LN i34EN 3#11 i34EN 3#LL i34ES L#FL i34ES O#PL i34ES

N2 ? C0? C,0 7 &

I >

( % ! ! !B 2

? W34iσX)# 2 σ $ ) $

(68)

N3

* *

,WL ,WL

"

C0? 3#FT i34EF 3#S3 i34EF 3#SL i34EF 3#SO i34EF 3#SS i34EF

C,0 F#P1 i34EN O#4F i34EN F#P i34ES P#4F i34ES L#4S i34EF

O2 ? % ! C0? C,0 7 & , 8 ( < ! & ( 2 C0?Q X ?R QVR 4#N N#4P 3#4 L#SS L#4 F#43 L#N F#FO L#PN F#TL P2 - C0?& C,0Q X ?R QVR 4#44NN T#FLF 4#4NN 1#FN 4#L S#4PF 4#LN L#3FO 4#F 3#L41 T2 - C,0& LE" B Q X ?R QVR 4#N N#4P 3#4 L#SS L#4 F#43 L#N F#FO L#PN F#TL 12 - LE" B

(69)

NL C,0U LE" B Q X ?R QVR 4#44NN T#43 4#4NN O#S4 4#4P L#OS 4#L L#NS 4#F P#T4

342 - C,0U LE" B &

/ = ( < $ ! . > ! & 2 C0?Q X ?R QVR 4#N T#PF 3 S#34 L F#43 332 8 $ C0?& C,0Q X ?R QVR 4#44NN P#L4 4#L F#33 4#F L#FT 3L2 8 $ C,0& < ( < C,0 ! $ !B 2 V- W^ QM XM 8R XQM XM 8R B _i344 F > . 7 7 & ( 8 ,#T4 K 3L4V^S3_&

(70)

NF C,0Q X ?R * QVR 4#44NN 34O#TF 4#L 1F#3N 4#F TL#TP 3F2 * C,0 & C,0Q X ?R * QVR 4#44NN 33P#SF 4#L T4#PT 4#F TL#TT 3S2 * C,0 , WL& C,0Q X ?R * QVR 4#44NN 34P#T3 4#L 1F#33 4#F TF#O1 3N2 * C,0 & C,0Q X ?R * QVR 4#44NN 331#L3 4#L T4#43 4#F T3#FO 3O2 * C,0 , WL& C,0Q X ?R * QVR 4#44NN 33S#TS 4#L T3#1F 4#F TN#3N 3P2 * C,0 " & C0? ! 7 & ) ! PP#LOV& ( < ! !B 2 V- 2 ^QM R XQM R _i344 ( < C0?! 7 C,0& ( # 8 ,#T4 K 3L4V^S3_2

(71)

NS C0?Q X ?R * QVR 4#N TT#1L 3 11#1P L 344#SL 3T2 * C0? & C0?Q X ?R * QVR 4#N 14#PT 3 34L#FO L 1T#L4 312 * C0? , WL& C0?Q X ?R * QVR 4#N 14#3L 3 1S#F4 L 1T#FT L42 * C0? & C0?Q X ?R * QVR 4#N 1N#4L 3 1T#T L 34L#TL L32 * C0? , WL& C0?Q X ?R * QVR 4#N T1#PO 3 11#11 L 34L#LL LL2 * C0? " &

(72)

NN 3939 0 8 = 0 ; + C,0 C0? > B B $ CE* $ 7 # # ! ! ! #% $ C,0 ! # ! & " B % ! % $ B % CE* & ! #$ " ! $ Q OTR& OT2 ! $ C,0 & " B # ! B % > $ $ C,0# ; # - ! C0?Q O1# P4#P3#PS PNR&

(73)

NO

O12 E" > CE* 7

" Q-C0?WT#FF R&

P42 E" > CE* 7

" Q-C0?WT#F3 R&

C,0 > # 7 # # $

(74)

NP " ! $ C,0 C0? > CE* 7 " & * ! . ! # ! $ C,0 C0? ! ; 7 > & + ! ! < & #! > ! " 7 # ; & P3#PL PF ; E"

!B # ; LN4Y #3N4Y T4Y #

&

P32 E" !B Q

(75)

NT PL2 E" !B Q ; W3N4Y Z-C0?WT#31 Z-G C,0W1#NP R& PF2 E" !B Q ; WT4Y Z-G C,0W1#O4 R& PS#PN PO ; E" !B LN4Y #

(76)

N1

PS2 E" !B Q

; WLN4Y Z-C0?WT#L3 R&

PN2 E" !B Q

(77)

O4 PO2 E" !B Q ; WT4Y Z-C0?WT#4P Z-G C,0WT#TL R& ! " B ! $ C,0 C0? % > ! 7 # % ! ! . ; & # # $ #% $ #% $ C,0#$ ! C0?& @ T4Y $ ; ! 7 $ $ 7 & $ ! . 7 $ C,0 ; ! & # E > $ !B #

ELE % ! ; ; LN4Y #3N4Y

T4Y & E !

# !B # ELE &

PP TT

(78)

O3

PP2 E" Q

; WLN4Y Z-C0?WT#LF R&

PT2 E" Q ;

(79)

OL

P12 E" Q ;

T4Y Z-G C,0W1#NO R&

T42 E" ELE Q ;

(80)

OF

T32 E" ELE Q ;

3N4Y Z-C0?WT#F3 Z-G C,0W1#P4 R&

TL2 E" ELE Q ;

(81)

OS

TF2 E" Q ;

LN4Y Z-C0?WT#F3 R&

TS2 E" Q ;

(82)

ON

TN2 E" Q ;

T4Y Z-G C,0WT#TT R&

TO2 E" ELE Q ;

(83)

OO TP2 E" ELE Q ; 3N4Y Z-C0?WT#S4 Z-G C,0WT#1O R& TT2 E" ELE Q ; T4Y Z-G C,0WT#OT R& ! 7 7 & # !B # # 3N4Y # E 7 $ % % & ( $

(84)

OP $ ! C0? 3N4Y $ $ 7 !B % & ! . 7 !B " 7 !B % #; 7 ^SL_& ( $ ELE Q T4 TL TO TTR % LN4Y 3N4Y 7 #

3N4Y & T4Y #

! $ C0?$ ! # ! ! & * ! % ; QT4Y R $ % ELE QTL#NY R ! 7 ! & ( % $ > CE* 7 " & ( ! # ! ! &

(85)

OT

0 8 ///

(86)

O1 49 0 ( C,0 # C0?# < ! % B B & ! E $ 2 E" E " & + " ! 7

E" E" &

< ! ! 7 $ B % " & C,0 C0? > B B % < ! $ C,0& ! % " C,0 C0? % $ ! ,& # > B B E % , WL C,0 C0?$ % % , $ & C,0 C0? ! # " # ! & + " ! $ ! # ! 7 $ C,0 ; CE* & * 7 ; 7 & # 7 $ !B % ELE &

(87)

P4

59 + >

3& d,(& + ! :" ) & C 2

d , " ( 7 Qd,(RZL44S&

L& +8 & +8 8! 2 QC,0#9 # - ": R& +

8 ! ZL44T ^ 4TXL44TZ L441 F4X4PXL441_Z

! 2" 2XXIII& & X !! X &" &

F& , 6#( 7I H #) ! -& C,0 C0?2 *

) :&82 * # & * " & ? 2 *

! ZL44T& & 3 E FL&

S& # # +# #C C?# C& C E

,: : : QC,0R " j " E

! & " & L44T ZSLQLR234PE3F&

N& ? # #C 6#C !!" --& 8 E": : :

QC,0R " : Qb: cR2 !! "

& " & L441Z34SQ3ELR23E34&

O& * & ) : " & 82 * # &

? 2 * ! ZL44T& & 3 E31&

P& 0 6#) --& !C E,: : : 5

H ( E - i&6 !! & L441ZNSQLR2FP4EN&

T& , : ) # ) # ) & " : ! E

": : : QC,0R E : QC0?R " &

6 ! ) & L44SZS1QOR23LL4E1&

1& " H8 2 * : ! " # # 0 & + I

6 :2 H k &# 8 &Z L44O& ! 2

" 2XX" H & !& X" H8 X & &

34& Hj : ! & ? 2 " ZL44P

^ L44P& ! 2III& & &

33& C 0# 7 #+ 6 & ^ E": : : _&

- + & L44O 6 3E3NZSFQ3R2F1EST&

3L& #, 6 #9 5# # : & ^ " ! E": : : QC,0R ! _& ) Q R& L44N ZL3QFR2LTSE1& 3F& ? 6#) H ) #d H & ! 2 I !" !! ! E": : : I " ! & * & 311T 6 ZF3QOR2PL1EFO&

(88)

P3

3S& )# #) # " )#0 # ! -# & C E

": : : QC,0R " 2 " : " H &

!" + Il H : !) & L44O Z34PS2NN1EPO&

3N& + " 9?#0 -?& C,02 I ! & "

& L443 6 3ZOFQ3R23ELL&

3O& 9 #l & C E": : : 2 &

" & 311T ZNFQ3LR2331NET&

3P& 5#* [#? " +& " ! E

": : : & ( " & L44O ZOQ3R2SSENL&

3T& - 6# " ,#C :*#l ,& ?% :2 IH "

! & 0 6 :" :&L44S Z3TS234SEO&

31& - B ] * Q* -R b: & ? 2 .

* $ ZL44P ^ 4LXL44PZ L44T 4LX4SXL44T_Z

! 2III& & & X" X X* -X: XFLS4NO 3& !&

L4& )# #0 # # +#? " 9# &

-: ! E": : : #! 7 # "

& 6 ! :" " :&L44P ZLPQOR2OLNEFT&

L3& 6# #?6& C E,: : QC,0R E *!! ,

! 0 " & ) - & L44LZ3S2343 E L3&

LL& *#9 d #L & C ": : : QC,0R &

* & L44L 6 Z1QPR2PF4E1& LF& d #L #+ 9& - ! E ": : : Q% bR " & & L44L 3TZ3LOQLR233SEP& LS& 0 #, (# ) & - # # % 7: E : ! E": : : QC,0R& 6 !! & L44S ZS1QLR2FP1ETP& LN& 0 # C#C -# # & ! E": : : ! : : " I "

& 6 !" ":&L44S NZT44Q3ELR2LF1ESS&

LO& 6d#( ! ?)#, !! 9+#)" H : #0 ) &

: ! E": : : E": : C X )

, ? & 6 ) & L44P ZNLQLR2FTFET&

LP& ) "& L44T ^ L44T L4X4FXL44T_Z ! 2

III& "& X X "X X)8C X,POL1&

LT& ) *& " + * C ! !, "

(89)

PL 3FN& C E0 : QC0?R& ) H" 2 + 8 !d H ?!Z L44S& L1& , : ) # ) # ) & " : ! E ": : : QC,0R E : QC0?R " & 6 !! & L44S + ZS1QOR23LL4E1&

F4& ) - d& ! " ":& ) 2

? :S Z ^ L44T LSX4FXL44T_Z ! 2

" 2XXIII& :S & X&

F3& )H #, # 6#+ # & 8 & N &

2 0 H ZL44L&

FL& - #0 # 0C# # ,#6 #8 ) # #? & 5

$ ! * ! $ & @ + & L44SZLPQNR2PP3 E T4&

FF& 9 C# ? 0)# *I +& C " ":

) :2 C & ) 2 Z311O&

FS& + *) & G 2 ) !& ) 2

) ZL44P&

FN& @0# ?C& $ , ? #

* $ 5 & ) 2 ) -ZL443&

FO& d H & : " ! , ? E L441 ^ L441

LNX41XL441_2 ! 2" 2XX"&IH & XIHX H2, ? & !&

FP& d ,,# #??# #6 #) # & 8 " !

: & P & 0 2 d I "Z31TT&

FT& 9 -& , H ! : 7 - & 3 & + Il H2

d :Z31P1&

F1& ( ) ?& C,0 ) < 0 B &

2 ZL441&

S4& 0 I , #9 : 9 & - *% " - !C E

0 : I " " & ): " !SE,: : : & "

6 !( " :&31OOZF3QLR2STNEP&

S3& 8 ,& 5 ! : 2 " : @LQ-3R&

8 ! , 7 ! " - % !

- ! " ! , & C 311O&

SL& d?*# " ??& ! ! : " N & I 2

Referências

Documentos relacionados

TOMATE MADURO, santa cruz (oblongo), 3a, com diâmetro equatorial maior que 70mm, com grau de maturação maduro, o lote devera apresentar homogeneidade visual de tamanho

A seguir, veremos algumas modificações para as estimativas dos limites frames A e B, onde são usadas diferentes funções wavelets, vy1,.... - Functional Analysis,

As lipases têm encontrado um vasto campo de atuação nas indústrias, sendo utilizada em diversas aplicações como no processamento de óleos e gorduras, formulação de detergentes,

«A deputada Sónia Nicolau diz que tudo o que promo- vermos para travar o aquecimento global será uma mais-valia para nós e para os nossos descendentes.. Ela reforçou a ideia de

• Pacientes imunossuprimidos – as vacinas utilizadas não contêm vírus vivo, são consideradas seguras e estão indicadas para este grupo de pacientes com maior risco

---- A Câmara deliberou, por unanimidade, emitir parecer favorável à pretensão, devendo o requerente proceder à sinalização dos trabalhos, precavendo a integridade de

O “salto”, categoria de Lukács para falar sobre a passagem da falsa para a verdadeira consciência, se verificou, pelas falas dos operários, na realização de uma greve por

Dentro da perspectiva de análise da mídia como uma instituição que traduz e dissemina o mundo simbólico em valores e normas para a sociedade, nelas incluídas